US3644318A - Process for the polymerization of olefins - Google Patents

Process for the polymerization of olefins Download PDF

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Publication number
US3644318A
US3644318A US836589A US3644318DA US3644318A US 3644318 A US3644318 A US 3644318A US 836589 A US836589 A US 836589A US 3644318D A US3644318D A US 3644318DA US 3644318 A US3644318 A US 3644318A
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magnesium
polymerization
suspension
catalyst
titanium
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Bernd Diedrich
Karl Diether Keil
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Hoechst AG
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Hoechst AG
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Priority claimed from DE19681795197 external-priority patent/DE1795197C2/de
Priority claimed from DE19691928772 external-priority patent/DE1928772C3/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst

Definitions

  • the present invention provides a process for polymerizing olefins in the presence of a mixed catalyst.
  • the catalysts used are prepared from mixtures of compounds of elements of sub-groups IV to VI of the Periodic Table and organo-metal compounds of elements of Groups I to III of the Periodic Table, and the polymerization is generally carried out in suspension, in solution or even in the gaseous phase.
  • 1,214,653 discloses a process for the preparation of supported catalysts, wherein pyrogenic metal or metalloid oxides, preferably pyrogenic alumina, pyrogenic titanium dioxide or pyrogenic silica, serving as carrier materials and the surfaces of which contain hydroxy groups, are reacted with determined heavy metal compounds of the metals of Groups, IVa, Va, VIa, VHa and VIII of the Periodic Table.
  • the medium particle size of the carrier material has to be inferior to about 0.1 micron and the concentration of hydroxy groups has to be such that the hydroxy groups react with at least 1 l0- equivalents of the transition metal per gram of carrier material.
  • the polymerization reactions according to the Ziegler process using supported catalysts are, how ever, easily carried out only if the polymers can be processed without having to remove the catalyst and carrier material. This is, however, only possible if high polymerization yields per catalyst unit are obtained; especially a high chlorine content in the polymer may cause decoloration of the product obtained or corrosion damage to the processing machines.
  • R stands for hydrogen or a hydrocarbon radical, preferably a straight-chain or
  • the process uses, as component A, a titanium-containing reaction product of magnesium alcoholates with a tetravalent halogenated titanium compound, unreacted magnesium alcoholate being likewise used for the polym erization.
  • the reaction product is a special type of a supported catalyst since the reaction brings about a close union between the magnesium alcoholate and the halogenated tetravalent titanium compound and alters structure of the reaction components.
  • transition metal compounds suitable for the preparation of component A there are used tetravalent halogenated titanium compounds, preferably titanium compounds of the general formula TiX,,(OR) in Which n is 1 to 4, X stands for chlorine or bromine, and R for identical or different hydrocarbon radicals, especially straight-chain or branched alkyl groups having 1 to 18, preferably 1 to 10, carbon atoms.
  • halogeno-ortho-titanic acid esters of the above formula in situ by reacting the respective ortho-titanic acid ester with TiCL, in a corresponding proportion.
  • the reaction is advantageously carried out at temperatures of from to 200 C., the upper temperature limit being determined by the decomposition temperature of the tetravalent halogenated titanium compound used, it is advantageously carried out at temperatures of from 60 to 120 C.
  • the reaction may be effected in inert diluents, for example aliphatic or cycloaliphatic hydrocarbons as are currently used for the low pressure process, such as butane, pentane, hexane, heptane, cyclohexane, methyl-cyclohexane as well as aromatic hydrocarbons, such as benzene or toluene; hydrogenated Diesel oil fractions which have been carefully freed from oxygen, sulfur compounds and moisture are also useful.
  • inert diluents for example aliphatic or cycloaliphatic hydrocarbons as are currently used for the low pressure process, such as butane, pentane, hexane, heptane, cyclohexane, methyl-cyclohexane as well as aromatic hydrocarbons, such as benzene or toluene; hydrogenated Diesel oil fractions which have been carefully freed from oxygen, sulfur compounds and moisture are also useful.
  • reaction product of magnesium alcoholate and tetravalent halogenated titanium compound which is insoluble in hydrocarbons is freed from unreacted titanium compound by washing it several times with one of the above inert diluents in which the titanium- (IV) compound used is readily soluble.
  • magnesium alcoholates preferably those of the general formula Mg(OR) are used, in which R stands for identical or different hydrocarbon radicals, preferably straight-chain or branched alkyl groups having 1 to carbon atoms; magnesium alcoholates having alkyl groups of from 1 to 4 carbon atoms are preferred. Examples thereof are Mg(OCH).
  • R stands for identical or different hydrocarbon radicals, preferably straight-chain or branched alkyl groups having 1 to carbon atoms; magnesium alcoholates having alkyl groups of from 1 to 4 carbon atoms are preferred. Examples thereof are Mg(OCH
  • the magnesium alcoholates can be prepared by known methods, for example by reacting magnesium with alcohols, especially monohydric aliphatic alcohols.
  • Magnesium alcoholates of the general formula XMgOR in which X stands for halogen, (80,) carboxylate, especially acetate or OH, and R has the above meaning, may also be used.
  • These compounds are, for example, obtained by reacting alcoholic solutions of the corresponding anhydrous acids with magnesium.
  • the titanium content of component A may be within the range of from 0.05 to 10 mg.-atom preferably from 1 to 10 mg.-atom, per gram of component A. It can be controlled by the reaction time, the reaction temperature and the concentration of the tetravalent halogenated titanium compound used.
  • the concentration of the titanium component fixed on the magnesium compound is advantageously in the range of from 0.005 to 1.5 mmols, preferably from 0.03 to 0.8
  • the magnesium alcoholate may be reacted with other inert inorganic solid substances which do not inhibit the p01ym erization, for example halides, sulfates, carbonates, phosphates, such as fluorides and chlorides, for example MgF MgCI AlCl ZnCl ,NiCl alkaline earth metal carbonates, for example BaCO alkaline earth metal phosphates, for example Ca (PO Especially advantages results are obtained, as disclosed in detail hereinafter, using, as inorganic solid substance that does not inhibit the polymerization, magnesium compounds containing hydroxy groups.
  • the molar ratio of magnesium alcoholate to the magnesium compound containing hydroxy groups may vary within wide limits.
  • Of advantage is a mixture of magnesium alcoholate and magnesium compound containing hydroxy groups in an amount of from 0.1 to 1.5 mols per gram-atom of magnesium.
  • the magnesium compounds containing hydroxy groups used are, for example, magnesium sulfates, carbonates, carboxylates, silicates, phosphates, all containing hydroxy groups, preferably Mg(OH)
  • the magnesium compounds containing hydroxy groups are prepared by known methods.
  • the magnesium alcoholate is ground with the magnesium compound containing hydroxy groups, for example in a ball mill, whereupon an intimately mixed solid material having a particle size distribution of from 1 to 150 is obtained.
  • a mixture of a magnesium alcoholate and a magnesium compound containing hydroxy groups may, however, also be prepared by reacting magnesium alcoholates with water or aqueous acids, for example sulfuric acid, carboxylic acids, phosphoric acid, hydrochloric acid.
  • the alcohols formed in the reaction can be eliminated by drying the reaction product.
  • the tetravalent titanium compound of component A is suitably converted during the polymerization into a compound having a lower valence and which is active for the polymerization by means of the organo-aluminum compound (component B) at temperatures of from 20 to 150 0., preferably from 50 to C.
  • component A with the organo-aluminum compound at temperatures of from 30 to 100 C., preferably from 0 to 20 C., prior to the polymerization and then to use it for the polymerization.
  • chlorinated organo-aluminum compounds it is however, suitable to wash the reaction product obtained and then to activate it by means of further organo-aluminum compound at temperatures of from 20 to 0., preferably from 50 to 100 C.
  • the organo-aluminum compounds used may be reaction products of aluminum-trialkyls or aluminum-dialkyl hydrides with hydrocarbon radicals having 1 to 16 carbon atoms, preferably Al(iBu) or A1(iBu) H and diolefins containing 4 to 20 carbon atoms, preferably isoprene; for example aluminum isoprenyl.
  • component B chlorinated organo-aluminum compounds, for example dialkyl-aluminum monochlorides of the formula R AlCl or alkylaluminum sesquichlorides of the formula R Al Cl in which formulae R stands for identical or dilferent hydrocarbon radicals, preferably alkyl groups having 1 to 16 carbon atoms, preferably 2 to 12 carbon atoms, for example (C2H5)2A1Cl, (C H Al Cl
  • component B aluminumtrialkyls of the formula AlR or aluminum-dialkyl hydrides of the formula AlR H, in which formulae R stands for identical or different hydrocarbons, preferably alkyl groups having 1 to 16, preferably 2 to 6, carbon atoms, for example Al(C2H5)3, Al(C2H5)2H, (C3H7)3' Al(C3H7)2H, O1
  • the organo-aluminum component may be used in a concentration of from 0.5 to 10 mmols, preferably from 2 to 4 mmols, per liter of dispersing agent or per liter of reactor volume.
  • the polymerization is carried out in solution, in suspension or in the gaseous phase, in continuous or discontinuous manner, at temperatures of from 20 to 150 C., preferably from 50 to 100 C.
  • the pressures are up to 50 atmospheres, preferably from 1.5 to 8 atmospheres. Generally, even higher or lower pressures and temperatures are also possible.
  • Suitable for the suspension polymerization are inert solvents currently used for the low-pressure process of Ziegler and specified in detail further above for the preparation of component A.
  • olefins of the general formula R-CH CH in which R stands for hydrogen or a hydrocarbon radical especially a straight-chain or branched substituted or unsubstituted alkyl group having 1 to 10, preferably 1 to 8 carbon atoms, for example ethylene, propylene, butene- (1), pentene-(l), 4-methylpentene-( 1) or octene- 1
  • R stands for hydrogen or a hydrocarbon radical especially a straight-chain or branched substituted or unsubstituted alkyl group having 1 to 10, preferably 1 to 8 carbon atoms, for example ethylene, propylene, butene- (1), pentene-(l), 4-methylpentene-( 1) or octene- 1
  • Mixtures of olefins of the above formula may also be used, especially those containing up to 10% by weight, preferably up to by weight, of one or more comonomers.
  • Ethylene or mixtures of ethylene with up to by weight, preferably up to 5% by weight, of a-olefins of the cited formula are preferably polymerized.
  • the molecular weights of the polymers can be controlled in known manner, preferably by means of hydrogen.
  • catalysts When catalysts are used, components A of which have been prepared by reacting chloroalkoxy-titanates-(IV) of the formula TiCl (0R) in which n is a number of 1.5 to 2.5 and R stands for identical or different alkyl groups having 2 to 8 carbon atoms, with a mixture of magnesium alcoholate and magnesium compounds containing hydroxy groups in an amount of from 0.1 to 1.5 mols per gramatom of magnesium, the Mw/Mn-values of the polymers can be controlled within a range of from 4 to 8 by means of the content of hydroxy groups in the mixture of the magnesium compounds.
  • Another advantage of the process of this invention is the preparation of polymers having a very narrow molecular weight distribution (Mw/Mn-values of from 2 to 4) and interesting technological properties, with the use of chloroalkoxy-titanates-(IV) of the formula TiCl (OR) in which n is 1 to 2 and R stands for identical or different alkyl groups having 2 to 8 carbon atoms.
  • the products obtained in this manner have excellent color and corrosion values and are especially suitable for the production of injection-molded articles.
  • EXAMPLE 1 (1) Preparation of supported catalyst 11 g. of Mg(OH H were suspended in 50 ml. of Diesel oil (boiling range of from to 160 C.) and 200 ml. of a l-molar solution of TiCl (OiC H-;) in cyclohexane were added. The suspension was refluxed for 7 hours. Subsequently, the precipitate was washed, by decanting and stirring, 6 times each with 150 ml. of cyclohexane. Care had to be taken that the cyclohexane overlying the solid substance was free from titanium compound. The volume of the suspension was completed to 250 ml.
  • the titanium content of the suspension was determined colorimetrically by means of hydrogen peroxide (cf. G.O. Miiller, Praktikum der quantitativen chemischen Analyse, 4th edition [1957], page 243). 10 ml. of the suspension contained 2.9 mmols of titanium compound.
  • Mw/Mnvalues were determined with the help of the fractionation data obtained by means of the gel permeation chromatograph of Messrs. Water (USA) in 1,2,3-trichlorobenzene as solvent and eluent at 130 C.
  • the polymer exhibited excellent color and corrosion values.
  • EXAMPLE 2 Copolymerization of ethylene and bntene-(l)
  • a 150 l.-vessel 100 l. of Diesel oil having a boiling range of from 140 to 200 C. were heated to 85 C. and the air was evacuated by flushing with pure nitrogen. Subsequently, a solution of 79.2 g. (400 mmols) of aluminumtriisobutyl in 500 ml. of Diesel oil and 70 ml. of a suspension of the supported catalyst (prepared according to 1 (1)) were added. The polymerization was carried out at 85 C. 6 kg. of ethylene and 180 g.
  • the titanium content of the suspension was determined colorimetrically by means of hydrogen peroxide.
  • the polyethylene formed was separated by filtration from the dispersing agent and dried. About 35 kg. of polyethylene having a reduced specific viscosity of 2.4 (measured on a 0.l%-solution in decahydronaphthalene at 135 C.) were obtained. The product exhibited excellent color and corrosion values.
  • the volume of the suspension was completed to 250 ml. Its titanium content was determined colorimetrically by means of hydrogen peroxide.
  • the precipitate was washed, by decanting and stirring, 6 times with 150 ml. of Diesel oil.
  • the Diesel oil overlying the solid material should be free from titanium compound.
  • the volume of the suspension was completed to 250 ml. Its titanium content was determined colorimetrically by means of hydrogen peroxide. 10 ml. of suspension contained 2.1 mmols of titanium compound.
  • EXAMPLE 6 Polymerization of ethylene in the gaseous phase 500 g. of polyethylene (reduced specific viscosity of 1.5, apparent density 450 g./l.) were introduced into a horizontal 10 l.-reactor provided with a stirrer, the stirring means of which scrape along the inner wall of the reactor. The reactor was freed from air by evacuating it several times and flushing it for several hours with a mixture of ethylene and hydrogen. Subsequently, the contents of the reactor were heated to 83 C. 5.7 g. of Al(C H (50 mols) and 17 ml. of suspension of the supported catalyst (prepared according to Example 1 (I)) were .fed in.
  • polyethylene reduced specific viscosity of 1.5, apparent density 450 g./l.
  • EXAMPLE 7 (I) Preparation of catalyst To prepare a mixture of magnesium-ethylate and magnesium hydroxide having a content of hydroxy groups of 0.2 mol per gram-atom of magnesium, 114.3 g. (1 mol) of magnesium-ethylate were combined with 3. 6 ml. (0.2 mol) of water and the mixture was then finely ground under exclusion of air and moisture.
  • the volume of the suspensoin was completed to 1,500 ml. Its titanium content was determined colorimetrically by means of hydrogen peroxide.
  • the polymer had a Mw/Mn-value of 4.2 and exhibited excellent color and corrosion values.
  • EXAMPLE 8 (I) Preparation of catalyst To prepare a mixture of magnesium-ethylene and magnesium hydroxide having a content of hydroxy groups of 1 mol per gram-atom of magnesium, 57 g. (0.5 mol) of magnesium ethylate and 29.2 g. (0.5 mol) of magnesium hydroxide were ground in a ball mill under exclusion of air and moisture.
  • the volume of the suspension was completed to 750 m1. Its titanium content was determined colorimetrically by means of hydrogen peroxide.
  • the polymer had a Mm/Mn-value of 5.6 and exhibited excellent color and corrosion values.
  • the volume of the suspension was completed to 750 ml. Its titanium content was determined colorimetrically by means of hydrogen peroxide.
  • titanium compound is titanium tetrachloride or chloroalkoxy-titanates of the formula TiCl,,(OR) in which n is 1 to 3 and R stands for identical or different straightchain or branched alkyl groups having 1 to 10 carbon atoms.
  • a process as claimed in claim 1 wherein the titanium content per gram of component A is from 0.05 to 10 mols.
  • component A is prepared by reacting the magnesium alcoholate with the titanium compound at temperatures of from 0 to 200 C.
  • organoaluminum compound is an aluminum-trialkyl of the formula Al(R) or an aluminum-dialkyl hydride of the formula Al(R) H where R stands for identical or different hydrocarbon radicals having 1 to 16 carbon atoms.
  • a process as claimed in claim 1 wherein the olefins polymerized are ethylene, propylene, butene-(l), pentene- 1 or 4-methyl-pentene-(1).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US836589A 1968-08-21 1969-06-25 Process for the polymerization of olefins Expired - Lifetime US3644318A (en)

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DE19681795197 DE1795197C2 (de) 1968-08-21 1968-08-21 Verfahren zur Polymerisation von -Olefinen
DE19691928772 DE1928772C3 (de) 1969-06-06 1969-06-06 Verfahren zur Polymerisation von alpha-Olefinen

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Cited By (89)

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DE2329641C3 (de) * 1973-06-09 1978-09-28 Hoechst Ag, 6000 Frankfurt Verfahren zur Polymerisation von ct-Olefinen
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DE2830929A1 (de) * 1978-07-14 1980-01-24 Basf Ag Verfahren zum herstellen einer titan-komponente fuer polymerisationskatalysatoren des ziegler-natta-typs
DE2831830A1 (de) * 1978-07-20 1980-01-31 Basf Ag Verfahren zum herstellen einer komponente fuer polymerisationskatalysatoren
JPS5846205B2 (ja) * 1979-10-24 1983-10-14 三菱化学株式会社 オレフインの重合方法
DE3538099A1 (de) * 1985-10-26 1987-04-30 Ruhrchemie Ag Verfahren zur homo- und mischpolymerisation von olefinen
DE4017661A1 (de) * 1990-06-01 1991-12-05 Hoechst Ag Verfahren zur herstellung eines poly-1-olefins

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BE737778A (enrdf_load_stackoverflow) 1970-02-23
FR2016081A1 (enrdf_load_stackoverflow) 1970-04-30
YU34249B (en) 1979-04-30
CA919345A (en) 1973-01-16
AT291559B (de) 1971-07-26
ES370632A1 (es) 1971-05-01
RO61993A (fr) 1978-05-15
NL152568C (nl) 1981-01-15
GB1275142A (en) 1972-05-24
FI51708B (enrdf_load_stackoverflow) 1976-11-30
FI51708C (fi) 1977-03-10
YU212269A (en) 1978-10-31
CS154641B2 (enrdf_load_stackoverflow) 1974-04-30
SE371200B (enrdf_load_stackoverflow) 1974-11-11
NO132871C (enrdf_load_stackoverflow) 1976-01-21
CH524645A (de) 1972-06-30
NL152568B (nl) 1977-03-15
BG17335A3 (bg) 1973-07-25
NO132871B (enrdf_load_stackoverflow) 1975-10-13
NL6912466A (enrdf_load_stackoverflow) 1970-02-24

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